Photostable compositions comprising para-alkoxyl phenyl substituted propenoic acid (APP) copolymer derivatives

ABSTRACT

The present disclosure relates, according to some embodiments, to photostable photoactive compositions comprising (a) at least one photoactive compound that develops within itself an excited state energy when subjected to UV radiation and (b) a block copolymer comprising a plurality of blocks, wherein the block copolymer is operable to quench the excited state energy.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Application No. 62/359,539,filed Jul. 7, 2016, which is incorporated by reference in its entiretyby reference.

FIELD OF THE DISCLOSURE

The present disclosure relates to photostable photoactive compositionscomprising para-alkoxyl phenyl substituted propenoic acid (APP)copolymer derivatives. Furthermore, the present disclosure relates tomethods of photostabilizing photoactive compositions comprising an APPcopolymer derivative.

BACKGROUND OF THE DISCLOSURE

Increased public awareness regarding the hazards associated withexposure of human skin to ultraviolet (UV) radiation has contributed tothe increasing popularity of UV-absorbing or scattering compounds(sunscreens), both independently and as a component of cosmeticproducts. However, the effectiveness of sunscreen products is directlylinked to the efficiency of photo absorption/scattering in the UV rangeof electromagnetic radiation, in particular, UV-B (280-320 nm) and UV-A(320-400 nm).

Amongst the most widely used combinations of UV-absorbing compoundsmarketed today is 4-tert-butyl-4-methoxy-dibenzoylmethane (BMDBM) andoctyl methoxycinnamate (OMC). Dibenzoylmethane derivatives, includingBMDBM, are commonly selected as sunscreen components based on theirability to absorb the full spectrum of UV-A radiation (320-400 nm).Similarly, OMC is known for effectively absorbing electromagneticradiation in the UV-B range (280-320 nm). However, neither compoundalone or in combination is ideal due to their known photo-instability.

Exposure of a dibenzoylmethane derivative to UV-A radiation causes theexcitation of an electron in the dibenzoylmethane derivative moleculefrom an initially occupied, lower energy orbital to a higher energy,previously unoccupied orbital. See Turro, Modern MolecularPhotochemistry, 1991. In the electronically excited state, thedibenzoylmethane derivative is prone to degrade via the number of knownpathways producing non-UVA-absorbing species and, therefore, can absorblittle or no additional UVA energy. Similarly, exposure of OMC to UVradiation transforms the compound into a less absorbing cis-isomer, andthereby less effective at rendering UV absorption. Furthermore, when adibenzoylmethane derivative (e.g., BMDBM) and OMC are exposed togetherto UV radiation, a photo reaction, known as the de Mayo reaction, occursbetween the species resulting in the rapid disappearance of both speciesand, consequently, a loss of photoprotective effect.

To photostabilize an electronically excited UV-absorbing organicmolecule (e.g., BMDBM), it must be returned to the ground state beforeit can undergo a photochemical reaction that is destructive to its UVradiation absorbing capabilities.

SUMMARY

Consequently, a need exists for an effective and safe light absorbingcomposition that is photochemically stable. Furthermore, a need existsfor a composition capable of effectively photostabilizing photoactivecompounds comprising dibenzoylmethane derivatives (e.g., BMDBM), OMC,and combinations thereof.

The present disclosure relates, in some embodiments, to photostablephotoactive compositions comprising (a) at least one photoactivecompound that develops within itself an excited state energy whensubjected to UV radiation, and (b) a block copolymer comprising aplurality of blocks, and may have a structure according to Formula 1:H₃C-V-W-X-Y-Z—CH₃,wherein the plurality of blocks comprises at least one block having astructure according to Formula II:

wherein R is C₁-C₃₀ alkyl; R₁ is selected from a group consisting of H,OH, and C₁-C₁₅ alkoxyl; R₂ is selected from a group consisting of H andC₁-C₁₅ alkyl; K is C1-C15 alkyl; B is selected from a group consistingof O and S; A is selected from a group consisting of CN and(C═O)NR₃(R₄); and each stereoisomer is selected from a group consistingof E, Z, R, S, and a combination thereof, wherein the block copolymer isoperable to quench the excited state energy. According to someembodiments, R₃ and R₄ are independently C₁-C₁₅ alkyl; wherein n is anumber from 1 to 5,000; wherein m is a number from 0 to 20; and whereinR, R₁, R₂, R₃, and R₄ may be either straight chain or branched chain.According to some embodiments, at least one block may have a structureaccording to Formula III:

wherein R₅ is C₁-C₃₀ alkyl; R₆ is selected from a group consisting of Hand C₁-C₁₅ alkyl; L is C₁-C₁₅ alkyl; D is selected from a groupconsisting of O and S; C is selected from a group consisting of CN and(C═O)NR₇(R₈); and each stereoisomer is selected from a group consistingof E, Z, R, S, and a combination thereof; wherein R₇ and R₈ areindependently C₁-C₁₅ alkyl; wherein o is a number from 1 to 5,000;wherein p is a number from 0 to 20; and wherein R₅, R₆, R₇ and R₈ may beeither straight chain or branched chain. According to some embodiments,at least one block may have a structure according to Formula IV:

wherein R₉ and R₁₀ are independently C₁-C₁₅ alkyl, and E is selectedfrom a group consisting of O and S; wherein q is a number from 1 to5,000; and wherein r is a number from 0 to 20. According to someembodiments, at least one block may have a structure according toFormula V:

wherein F is selected from a group consisting of O and S; wherein s is anumber from 1 to 5,000; and wherein t is a number from 0 to 20. In someembodiments, at least one block may have a structure according toFormula VI:

wherein R₁₁ and R₁₂ are independently C₁-C₁₅ alkyl, and G is selectedfrom a group consisting of O and S; wherein u is a number from 1 to5,000; and wherein v is a number from 0 to 20. In some embodiments,R₉═R₁₀, or R₁₁═R₁₂, but not both.

According to some embodiments, a block copolymer may be present at aconcentration of from about 1% by weight to about 20% by weight, basedon a total weight of a composition. For example, a block copolymer maybe present at a concentration of from about 0.000001% by weight to about20% by weight, based on a total weight of a composition. A blockcopolymer may be present at a concentration comprising about 15% byweight, about 10% by weight, about 5% by weight, about 1% by weight,about 0.000001% by weight, and a combination thereof, based on a totalweight of a composition.

According to some embodiments, the present disclosure relates tophotostable photoactive compositions, wherein at least one photoactivecompound comprises 4-methyldibenzoylmethane and derivatives thereof;octyl methoxycinnamate and derivatives thereof; octocrylene andderivatives thereof; p-methoxycinnamic acid esters and derivativesthereof; 1-(4-methoxyphenyl)-3-(4-tert-butylphenyl)propane-1,3-dione andderivatives thereof; oxybenzone and derivatives thereof;bis-ethylhexyloxyphenol methoxyphenyl triazone and derivatives thereof;methylene bis-benzotriazolyl tetramethylbutylphenol and derivativesthereof; 4-methylbenzylidene camphor and derivatives thereof;diethylamino hydroxyl benzoyl hexyl benzoate and derivatives thereof;drometrizole trisiloxane and derivatives thereof; ethylhexyl triazone,diethylhexyl butamido triazone and derivatives thereof;terephthalylidene dicamphor sulfonic acid, its salts, and derivativesthereof, menthyl anthranilate and derivatives thereof; retinol andderivatives thereof; coenzyme Q and derivatives thereof; cholecalciferoland derivatives thereof; porphyrin and derivatives thereof, resveratroland derivatives thereof; p-aminobenzoic acid, its salts, and derivativesthereof; glyceryl esters; anthranilate and derivatives thereof; cinnamicacid and derivatives thereof, coumarin and derivatives thereof;trihydroxycinnamic acid and derivatives thereof; dibenzalacetonenaphtholsulfonate, its salts, and derivatives thereof; dibenzalacetoneand derivatives thereof; dihydroxy-naphthoic acid, its salts, andderivatives thereof; o-hydroxydiphenyldisulfonate, its salts, andderivatives thereof; diazole derivatives; quinine derivatives, itssalts, and derivatives thereof; quinoline derivatives;hydroxyl-substituted benzophenone derivatives; quinolone derivatives;benzophenone derivatives; uric acid derivatives; quinine salts;hydroxydiphenyldisulfonate, its salts, and derivatives thereof; tannicacid and derivatives thereof; violuric acid and derivatives thereof;phenylbenzimidazole tetrasulfonate, its salts, and derivatives thereof;terephthalylidene dicamphor sulfonic acid, its salts, and derivativesthereof; benzalacetophenone naphtholsulfonate, its salts, andderivatives thereof; benzoic acid, its salts, and derivatives thereof;o-hydroxydiphenyldisulfonate, its salts, and derivatives thereof;p-naphthalate derivatives; methoxy-substituted uric acid derivatives;hydroquinone, its salts, and derivatives thereof; benzophenonederivatives; dihydroxycinnamic acid, its salts, and derivatives thereof;1, 3, 5-triazine derivatives; methylene bis-benzotriazolyltetramethylbutylphenol, its salts, and derivatives thereof; titaniumdioxide and derivatives thereof; triazole and derivatives thereof; zincoxide; bis-ethylhexyloxyphenol methoxyphenyl triazine and its salts;salicylate and derivatives thereof; diethylamino hydroxyl benzoyl hexylbenzoate, its salts, and derivatives thereof; and combinations of theforegoing.

The present disclosure relates, in some embodiments, to photostablephotoactive compositions, wherein at least one photoactive compound maybe present at a concentration of from about 1% by weight to about 20% byweight, based on a total weight of a composition. In some embodiments,at least one photoactive compound may be present at a concentrationcomprising about 15% by weight, about 10% by weight, about 5% by weight,about 1% by weight, or a combination thereof, based on a total weight ofa composition. A composition may include an oil phase having adielectric constant of at least about 8. A composition may include anoil phase having a dielectric constant of at least about 7.

In some embodiments, a composition may enhance protection of at leastone polymer against UV radiation, the at least one polymer comprisingpolyvinyl chloride, polystyrene, low-density polyethylene, high-densitypolyethylene, polyamides, nylon, polypropylene, rubber, and cellulose.According to some embodiments, a composition may enhance protection ofat least one coating against UV radiation, the at least one coatingcomprising adhesives, acrylic paint, latex paint, stains, caulk,sealants, urethanes, enamels, films, and inks. A composition may enhanceprotection of a sunscreen against UV radiation, wherein application of asunscreen to a skin of an animal (e.g., human) may protect a skinagainst UV radiation. In some embodiments, application of a coating to asurface (e.g., polymer, metal, canvas, or wood) may protect the surfaceagainst UV radiation.

The present disclosure relates, in some embodiments, to methods ofphotostabilizing photoactive compositions containing a block copolymerand at least one photoactive compound, the method comprising (a) addingat least one photoactive compound that develops within itself an excitedstate energy when subjected to UV radiation; and (b) adding the blockcopolymer in an effective amount to the composition, wherein the blockcopolymer is operable to quench the excited state energy; and whereinthe photoactive composition protects a substrate from oxidative stresscaused by absorption of light having a wavelength in the wavelengthrange from about 280 nm to about 400 nm. According to some embodiments,a block copolymer may comprise a plurality of blocks, and has astructure according to Formula I:H₃C-V-W-X-Y-Z—CH₃wherein the plurality of blocks comprises at least one block having astructure according to Formula II:

wherein R is C₁-C₃₀ alkyl; R₁ is selected from a group consisting of H,OH, and C₁-C₁₅ alkoxyl; R₂ is selected from a group consisting of H andC₁-C₁₅ alkyl; K is C1-C15 alkyl; B is selected from a group consistingof O and S; A is selected from a group consisting of CN and(C═O)NR₃(R₄); and each stereoisomer is selected from a group consistingof E, Z, R, S, and a combination thereof, wherein the block copolymer isoperable to quench the excited state energy. According to someembodiments, R₃ and R₄ are independently C₁-C₁₅ alkyl; wherein n is anumber from 1 to 5,000; wherein m is a number from 0 to 20; and whereinR, R₁, R₂, R₃, and R₄ may be either straight chain or branched chain.According to some embodiments, at least one block may have a structureaccording to Formula III:

wherein R₅ is C₁-C₃₀ alkyl; R₆ is selected from a group consisting of Hand C₁-C₁₅ alkyl; L is C₁-C₁₅ alkyl; D is selected from a groupconsisting of O and S; C is selected from a group consisting of CN and(C═O)NR₇(R₈); and each stereoisomer is selected from a group consistingof E, Z, R, S, and a combination thereof; wherein R₇ and R₈ areindependently C₁-C₁₅ alkyl; wherein o is a number from 1 to 5,000;wherein p is a number from 0 to 20; and wherein R₅, R₆, R₇ and R₈ may beeither straight chain or branched chain. According to some embodiments,at least one block may have a structure according to Formula IV:

wherein R₉ and R₁₀ are independently C₁-C₁₅ alkyl, and E is selectedfrom a group consisting of O and S; wherein q is a number from 1 to5,000; and wherein r is a number from 0 to 20. According to someembodiments, at least one block may have a structure according toFormula V:

wherein F is selected from a group consisting of O and S; wherein s is anumber from 1 to 5,000; and wherein t is a number from 0 to 20. In someembodiments, at least one block may have a structure according toFormula VI:

wherein R₁₁ and R₁₂ are independently C₁-C₁₅ alkyl, and G is selectedfrom a group consisting of O and S; wherein u is a number from 1 to5,000; and wherein v is a number from 0 to 20. In some embodiments,R₉═R₁₀, or R₁₁═R₁₂, but not both.

In some embodiments, the present disclosure relates to methods ofphotostabilizing photoactive compositions containing a block copolymerand at least one photoactive compound, wherein a substrate comprises asunscreen, a cosmetic, a polymer, and a coating. In some embodiments,application of a sunscreen to a skin of an animal (e.g., human) mayprotect the skin against UV radiation. A polymer may comprisehigh-density polyethylene, low-density polyethylene, polystyrene,polyamides, nylon, polypropylene, rubber, cellulose, polyvinyl chloride,and polyvinyl alcohol. According to some embodiments, a coating maycomprise stains, caulk, sealants, urethanes, enamels, films, adhesives,acrylic paints, latex paints, and inks. In some embodiments, a blockcopolymer may be present at a concentration from about 1% by weight toabout 20% by weight, based on a total weight of a composition. Forexample, a block copolymer may be present at a concentration from about0.000001% by weight to about 20% by weight, base on a total weight of acomposition. In some embodiments, a block copolymer is present at aconcentration comprising about 15% by weight, about 10% by weight, about5% by weight, about 1% by weight, or a combination thereof, based on atotal weight of a composition.

According to some embodiments, the present disclosure relates to methodsof photostabilizing photoactive compositions containing a blockcopolymer and at least one photoactive compound, wherein the at leastone photoactive compound comprises 4-methyldibenzoylmethane andderivatives thereof; octyl methoxycinnamate and derivatives thereof;octocrylene and derivatives thereof; p-methoxycinnamic acid esters andderivatives thereof;1-(4-methoxyphenyl)-3-(4-tert-butylphenyl)propane-1,3-dione andderivatives thereof; oxybenzone and derivatives thereof;bis-ethylhexyloxyphenol methoxyphenyl triazone and derivatives thereof;methylene bis-benzotriazolyl tetramethylbutylphenol and derivativesthereof; 4-methylbenzylidene camphor and derivatives thereof;diethylamino hydroxyl benzoyl hexyl benzoate and derivatives thereof;drometrizole trisiloxane and derivatives thereof; ethylhexyl triazone,diethylhexyl butamido triazone and derivatives thereof;terephthalylidene dicamphor sulfonic acid, its salts, and derivativesthereof, menthyl anthranilate and derivatives thereof; retinol andderivatives thereof; coenzyme Q and derivatives thereof; cholecalciferoland derivatives thereof; porphyrin and derivatives thereof, resveratroland derivatives thereof; p-aminobenzoic acid, its salts, and derivativesthereof; glyceryl esters; anthranilate and derivatives thereof; cinnamicacid and derivatives thereof, coumarin and derivatives thereof;trihydroxycinnamic acid and derivatives thereof; dibenzalacetonenaphtholsulfonate, its salts, and derivatives thereof; dibenzalacetoneand derivatives thereof; dihydroxy-naphthoic acid, its salts, andderivatives thereof; o-hydroxydiphenyldisulfonate, its salts, andderivatives thereof; diazole derivatives; quinine derivatives, itssalts, and derivatives thereof; quinoline derivatives;hydroxyl-substituted benzophenone derivatives; quinolone derivatives;benzophenone derivatives; uric acid derivatives; quinine salts;hydroxydiphenyldisulfonate, its salts, and derivatives thereof; tannicacid and derivatives thereof; violuric acid and derivatives thereof;phenylbenzimidazole tetrasulfonate, its salts, and derivatives thereof;terephthalylidene dicamphor sulfonic acid, its salts, and derivativesthereof; benzalacetophenone naphtholsulfonate, its salts, andderivatives thereof; benzoic acid, its salts, and derivatives thereof;o-hydroxydiphenyldisulfonate, its salts, and derivatives thereof;p-naphthalate derivatives; methoxy-substituted uric acid derivatives;hydroquinone, its salts, and derivatives thereof; benzophenonederivatives; dihydroxycinnamic acid, its salts, and derivatives thereof;1, 3, 5-triazine derivatives; methylene bis-benzotriazolyltetramethylbutylphenol, its salts, and derivatives thereof; titaniumdioxide and derivatives thereof; triazole and derivatives thereof; zincoxide; bis-ethylhexyloxyphenol methoxyphenyl triazine and its salts;salicylate and derivatives thereof; diethylamino hydroxyl benzoyl hexylbenzoate, its salts, and derivatives thereof; and combinations of theforegoing.

In some embodiments, the present disclosure relates to methods ofphotostabilizing photoactive compositions containing a block copolymerand at least one photoactive compound, wherein the at least onephotoactive compound may be present at a concentration of from about0.000001% by weight to about 20% by weight, based on a total weight of acomposition. In some embodiments, at least one photoactive compound maybe present at a concentration comprising about 15% by weight, about 10%by weight, about 5% by weight, about 1% by weight, about 0.5% by weight,about 0.1% by weight, or a combination thereof, based on a total weightof a composition. A photoactive composition may include an oil phasehaving a dielectric constant of at least about 7. A photoactivecomposition may include an oil phase having a dielectric constant of atleast about 8. In some embodiments, application of a cosmetic to a skinor a hair of an animal (e.g., human) thereby may protect the skin or thehair against UV radiation. Application of a sunscreen comprising aphotoactive composition to a skin of an animal (e.g., human) may protectthe skin against UV radiation.

The present disclosure, in some embodiments, relates to cosmetic ordermatological compositions for coating a skin to protect the skin fromoxidative stress caused by adsorption of light having a wavelength inthe wavelength range of about 280 nm to about 400 nm, the compositioncomprising (a) at least one photoactive compound that develops withinitself an excited state energy when subjected to UV radiation and (b) ablock copolymer comprising a plurality of blocks, having a structureaccording to Formula I:H₃C-V-W-X-Y-Z—CH₃wherein the block copolymer is operable to quench the excited stateenergy, and wherein the plurality of blocks comprises at least one blockhaving a structure according to Formula II:

wherein R is C₁-C₃₀ alkyl; R₁ is selected from a group consisting of H,OH, and C₁-C₁₅ alkoxyl; R₂ is selected from a group consisting of H andC₁-C₁₅ alkyl; K is C₁-C₁₅ alkyl; B is selected from a group consistingof O and S; A is selected from a group consisting of CN and(C═O)NR₃(R₄); and each stereoisomer is selected from a group consistingof E, Z, R, S, and a combination thereof, wherein the block copolymer.According to some embodiments, R₃ and R₄ are independently C₁-C₁₅ alkyl;wherein n is a number from 1 to 5,000; wherein m is a number from 0 to20; and wherein R, R₁, R₂, R₃, and R₄ may be either straight chain orbranched chain. According to some embodiments, at least one block mayhave a structure according to Formula III:

wherein R₅ is C₁-C₃₀ alkyl; R₆ is selected from a group consisting of Hand C₁-C₁₅ alkyl; L is C₁-C₁₅ alkyl; D is selected from a groupconsisting of O and S; C is selected from a group consisting of CN and(C═O)NR₇(R₈); and each stereoisomer is selected from a group consistingof E, Z, R, S, and a combination thereof; wherein R₇ and R₈ areindependently C₁-C₁₅ alkyl; wherein o is a number from 1 to 5,000;wherein p is a number from 0 to 20; and wherein R₅, R₆, R₇ and R₈ may beeither straight chain or branched chain. According to some embodiments,at least one block may have a structure according to Formula IV:

wherein R₉ and R₁₀ are independently C₁-C₁₅ alkyl, and E is selectedfrom a group consisting of O and S; wherein q is a number from 1 to5,000; and wherein r is a number from 0 to 20. According to someembodiments, at least one block may have a structure according toFormula V:

wherein F is selected from a group consisting of O and S; wherein s is anumber from 1 to 5,000; and wherein t is a number from 0 to 20. In someembodiments, at least one block may have a structure according toFormula VI:

wherein R₁₁ and R₁₂ are independently C₁-C₁₅ alkyl, and G is selectedfrom a group consisting of O and S; wherein u is a number from 1 to5,000; and wherein v is a number from 0 to 20. In some embodiments,R₉═R₁₀, or R₁₁═R₁₂, but not both.

According to some embodiments, the present disclosure relates tocosmetic or dermatological compositions for coating a skin to protectthe skin from oxidative stress caused by adsorption of light having awavelength in the wavelength range of about 280 nm to about 400 nm,wherein a skin surface comprises human skin and animal skin. In someembodiments, a block copolymer is present at a concentration of about 1%to about 20% by weight, based on a total weight of a composition. Ablock copolymer may be present at a concentration comprising about 15%by weight, about 10% by weight, about 5% by weight, about 1% by weight,about 0.000001% by weight, or a combination thereof, based on a totalweight of a composition.

In some embodiments, the present disclosure relates to cosmetic ordermatological compositions for coating a skin to protect the skin fromoxidative stress caused by adsorption of light having a wavelength inthe wavelength range of about 280 nm to about 400 nm, wherein the atleast one photoactive compound comprises 4-methyldibenzoylmethane andderivatives thereof; octyl methoxycinnamate and derivatives thereof;octocrylene and derivatives thereof; p-methoxycinnamic acid esters andderivatives thereof;1-(4-methoxyphenyl)-3-(4-tert-butylphenyl)propane-1,3-dione andderivatives thereof; oxybenzone and derivatives thereof;bis-ethylhexyloxyphenol methoxyphenyl triazone and derivatives thereof;methylene bis-benzotriazolyl tetramethylbutylphenol and derivativesthereof; 4-methylbenzylidene camphor and derivatives thereof;diethylamino hydroxyl benzoyl hexyl benzoate and derivatives thereof;drometrizole trisiloxane and derivatives thereof; ethylhexyl triazone,diethylhexyl butamido triazone and derivatives thereof;terephthalylidene dicamphor sulfonic acid, its salts, and derivativesthereof, menthyl anthranilate and derivatives thereof; retinol andderivatives thereof; coenzyme Q and derivatives thereof; cholecalciferoland derivatives thereof; porphyrin and derivatives thereof, resveratroland derivatives thereof; p-aminobenzoic acid, its salts, and derivativesthereof; glyceryl esters; anthranilate and derivatives thereof; cinnamicacid and derivatives thereof, coumarin and derivatives thereof;trihydroxycinnamic acid and derivatives thereof; dibenzalacetonenaphtholsulfonate, its salts, and derivatives thereof; dibenzalacetoneand derivatives thereof; dihydroxy-naphthoic acid, its salts, andderivatives thereof; o-hydroxydiphenyldisulfonate, its salts, andderivatives thereof; diazole derivatives; quinine derivatives, itssalts, and derivatives thereof; quinoline derivatives;hydroxyl-substituted benzophenone derivatives; quinolone derivatives;benzophenone derivatives; uric acid derivatives; quinine salts;hydroxydiphenyldisulfonate, its salts, and derivatives thereof; tannicacid and derivatives thereof; violuric acid and derivatives thereof;phenylbenzimidazole tetrasulfonate, its salts, and derivatives thereof;terephthalylidene dicamphor sulfonic acid, its salts, and derivativesthereof; benzalacetophenone naphtholsulfonate, its salts, andderivatives thereof; benzoic acid, its salts, and derivatives thereof;o-hydroxydiphenyldisulfonate, its salts, and derivatives thereof;p-naphthalate derivatives; methoxy-substituted uric acid derivatives;hydroquinone, its salts, and derivatives thereof; benzophenonederivatives; dihydroxycinnamic acid, its salts, and derivatives thereof;1, 3, 5-triazine derivatives; methylene bis-benzotriazolyltetramethylbutylphenol, its salts, and derivatives thereof; titaniumdioxide and derivatives thereof; triazole and derivatives thereof; zincoxide; bis-ethylhexyloxyphenol methoxyphenyl triazine and its salts;salicylate and derivatives thereof; diethylamino hydroxyl benzoyl hexylbenzoate, its salts, and derivatives thereof; and combinations of theforegoing.

In some embodiments, the present disclosure relates to cosmetic ordermatological compositions for coating a skin to protect the skin fromoxidative stress caused by adsorption of light having a wavelength inthe wavelength range of about 280 nm to about 400 nm, wherein at leastone photoactive compound may be present at a concentration of about0.000001% by weight to about 20% by weight, based on a total weight of acomposition. According to some embodiments, at least one photoactivecompound may be present at a concentration comprising about 15% byweight, about 10% by weight, about 5% by weight, about 1% by weight,about 0.5% by weight, about 0.1% by weight, or a combination thereof,based on a total weight of a composition. In some embodiments, acomposition may include an oil phase having a dielectric constant of atleast about 8. According to some embodiments, a composition may includean oil phase having a dielectric constant of at least about 7.

According to some embodiments, a block copolymer may be present at aconcentration from about 1% by weight to about 20% by weight, based on atotal weight of the composition. A block copolymer may be present at aconcentration comprising about 15% by weight, about 10% by weight, about5% by weight, about 1% by weight, or a combination thereof, based on thetotal weight of the composition. At least one photoactive compound maybe present at a concentration from about 0.000001% by weight to about20% by weight, based on the total weight of the composition. At leastone photoactive compound is present at a concentration comprising about15% by weight, about 10% by weight, about 5% by weight, about 1% byweight, about 0.5% by weight, about 0.1% by weight, or a combinationthereof, based on the total weight of the composition. A photostablephotoactive composition may include an oil phase having a dielectricconstant of at least about 7. A photostable photoactive composition mayinclude an oil phase having a dielectric constant of at least about 8. Aphotostable photoactive composition may enhance protection of at leastone polymer against UV radiation, the at least one polymer comprisingpolyvinyl chloride, polystyrene, low-density polyethylene, high-densitypolyethylene, polyamides, nylon, polypropylene, rubber, and cellulose.

At least one photoactive compound may comprise 4-methyldibenzoylmethaneand derivatives thereof; octyl methoxycinnamate and derivatives thereof;octocrylene and derivatives thereof; p-methoxycinnamic acid esters andderivatives thereof;1-(4-methoxyphenyl)-3-(4-tert-butylphenyl)propane-1,3-dione andderivatives thereof; oxybenzone and derivatives thereof;bis-ethylhexyloxyphenol methoxyphenyl triazone and derivatives thereof;methylene bis-benzotriazolyl tetramethylbutylphenol and derivativesthereof; 4-methylbenzylidene camphor and derivatives thereof;diethylamino hydroxyl benzoyl hexyl benzoate and derivatives thereof;drometrizole trisiloxane and derivatives thereof; ethylhexyl triazone,diethylhexyl butamido triazone and derivatives thereof;terephthalylidene dicamphor sulfonic acid, its salts, and derivativesthereof, menthyl anthranilate and derivatives thereof; retinol andderivatives thereof; coenzyme Q and derivatives thereof; cholecalciferoland derivatives thereof; porphyrin and derivatives thereof, resveratroland derivatives thereof; p-aminobenzoic acid, its salts, and derivativesthereof; glyceryl esters; anthranilate and derivatives thereof; cinnamicacid and derivatives thereof, coumarin and derivatives thereof;trihydroxycinnamic acid and derivatives thereof; dibenzalacetonenaphtholsulfonate, its salts, and derivatives thereof; dibenzalacetoneand derivatives thereof; dihydroxy-naphthoic acid, its salts, andderivatives thereof; o-hydroxydiphenyldisulfonate, its salts, andderivatives thereof; diazole derivatives; quinine derivatives, itssalts, and derivatives thereof; quinoline derivatives;hydroxyl-substituted benzophenone derivatives; quinolone derivatives;benzophenone derivatives; uric acid derivatives; quinine salts;hydroxydiphenyldisulfonate, its salts, and derivatives thereof; tannicacid and derivatives thereof; violuric acid and derivatives thereof;phenylbenzimidazole tetrasulfonate, its salts, and derivatives thereof;terephthalylidene dicamphor sulfonic acid, its salts, and derivativesthereof; benzalacetophenone naphtholsulfonate, its salts, andderivatives thereof; benzoic acid, its salts, and derivatives thereof;o-hydroxydiphenyldisulfonate, its salts, and derivatives thereof;p-naphthalate derivatives; methoxy-substituted uric acid derivatives;hydroquinone, its salts, and derivatives thereof; benzophenonederivatives; dihydroxycinnamic acid, its salts, and derivatives thereof;1, 3, 5-triazine derivatives; methylene bis-benzotriazolyltetramethylbutylphenol, its salts, and derivatives thereof; titaniumdioxide and derivatives thereof; triazole and derivatives thereof; zincoxide; bis-ethylhexyloxyphenol methoxyphenyl triazine and its salts;salicylate and derivatives thereof; diethylamino hydroxyl benzoyl hexylbenzoate, its salts, and derivatives thereof; and combinations of theforegoing.

According to some embodiments, a photostable photoactive composition mayenhance protection of at least one coating against UV radiation, the atleast one coating comprising adhesives, acrylic paint, latex paint,stains, caulk, sealants, urethanes, enamels, films, and inks. Aphotostable photoactive composition may enhance protection of asunscreen against UV radiation, wherein application of said sunscreen toa skin of an animal may protect the skin against UV radiation. Aphotostable photoactive composition may enhance protection of a cosmeticagainst UV radiation, wherein application of said cosmetic to a skin ora hair of an animal may protect the skin or the hair against UVradiation. Application of a coating to a surface may protect the surfaceagainst UV radiation. A substrate may comprise a sunscreen, a cosmetic,a polymer, and a coating. Application of a sunscreen to a skin of ananimal (e.g., human) may protect a skin against UV radiation. A polymermay comprise high-density polyethylene, low-density polyethylene,polystyrene, polyamides, nylon, polypropylene, rubber, cellulose,polyvinyl chloride, and polyvinyl alcohol. A coating may comprisestains, caulk, sealants, urethanes, enamels, films, adhesives, acrylicpaints, latex paints, and inks. Application of a cosmetic to a skin or ahair of an animal (e.g., human) may protect the skin or hair against UVradiation. Application of a sunscreen to a skin of an animal (e.g.,human) may protect the skin against UV radiation. A skin surfacecomprises human skin and animal skin.

BRIEF DESCRIPTION OF THE DRAWINGS

The file of this patent contains at least one drawing executed in color.Copies of this patent with color drawing(s) will be provided by thePatent and Trademark Office upon request and payment of the necessaryfee.

Some embodiments of the disclosure may be understood by referring, inpart, to the present disclosure and the accompanying drawings, wherein:

FIG. 1 is a graph illustrating the significant change in the UVradiation absorption spectra and decrease in UVA radiation absorptionwhen a composition comprising BMDBM and OMC according to an embodimentof the disclosure were irradiated with UV light;

FIG. 2 is a graph illustrating the UV radiation absorption spectra whena composition comprising BMDBM, OMC, and APP according to an embodimentof the disclosure were irradiated with UV light;

FIG. 3 is a graph illustrating the amount of BMDBM remaining in acomposition according to an embodiment of the disclosure afterirradiation with UV light;

FIG. 4 is a graph illustrating the phosphorescence spectra of APPanalogues and Avobenzone in ethanol glass at 77K;

FIG. 5 is a graph illustrating ketone triplet state quenching by APPanalogues as measured by a laser flash photolysis of a ketone in thepresence of varying concentrations of APP analogues in deoxygenatedacetonitrile solutions;

FIG. 6 is a set of graphs illustrating APP analogues quenching theketone triplet state by recovering the ground state of the ketone; and

FIG. 7 illustrates the ketone triplet state quenching rate constants ofvarious APP analogues.

DETAILED DESCRIPTION

The present disclosure relates, in some embodiments, to para-alkoxylphenyl substituted propenoic acid (APP) block copolymer derivativescapable of resolving excited energy states of certain photo unstablechromophores. Particularly, APP block copolymer derivatives may acceptenergy from electronically excited UV-radiation absorbing chromophoremolecules, such as dibenzoylmethane derivatives, such that an excitedstate of these UV-radiation absorbing molecules is photostabilized(i.e., returned to a ground state). Upon photostabilization, aUV-radiation absorbing chromophore molecule is preserved and may becapable of absorbing additional UV radiation. Accordingly, enhancedprotection of surfaces from UV radiation may be achieved by applyingcompositions comprising an APP block copolymer together withUV-absorbing materials (e.g., dibenzoylmethane derivatives). In someembodiments, a cosmetic, a sunscreen, a polymer (e.g., polyethylene),and/or a coating (e.g., paints) may comprise at least one APP blockcopolymer and at least one UV-absorbing compound, wherein applying thecosmetic, sunscreen, polymer, and/or coating to a surface (e.g., skin,hair, metal, polymer, plastic, canvas, or wood) may protect the appliedsurface from UV radiation.

This disclosure relates to sunscreen, cosmetic, polymer, coating, anddermatological compositions comprising a mixture of at least onephotoactive compound (e.g., BMDBM) that develops within itself anexcited state energy when subjected to UV radiation and at least one APPblock copolymer, wherein the APP block copolymer is operable to quenchthe excited state energy from an excited state energy acceptor. Thisdisclosure further relates to methods of photostabilizing a photoactivecomposition containing at least one photoactive compound and at leastone block copolymer that may function as an excited state energyacceptor. In some embodiments, a method comprises (a) adding the atleast one photoactive compound in an effective amount to a composition,wherein the at least one photoactive compound develops within itself anexcited state energy when subjected to UV radiation; and (b) adding theblock copolymer in an effective amount to the composition, wherein theblock copolymer comprises a plurality of blocks.

The present disclosure relates to photostable photoactive compositionsand methods of photostabilizing a photoactive composition. Compositionsmay comprise one or more photoactive compounds that may develop anexcited state when subjected to UV radiation. Photostable photoactivecompositions may also comprise an excited state energy acceptorcomprising an APP block copolymers comprising a plurality of blocks, andhaving a structure according to Formula I:H₃C-V-W-X-Y-Z—CH₃According to this disclosure APP block copolymers of Formula I arecapable of photostabilizing photoactive compositions by operating asexcited state energy acceptors/quenchers. However, this disclosure isnot limited to any particular mechanism by which APP block copolymers ofFormula I are capable of photostabilizing photoactive compositions.

In some embodiments an APP block copolymers may comprise a plurality ofblocks, wherein the plurality of blocks may comprise at least one blockhaving a structure according to Formula II:

wherein R is C₁-C₃₀ alkyl; R₁ is selected from a group consisting of H,OH, and C₁-C₁₅ alkoxyl; R₂ is selected from a group consisting of H andC₁-C₁₅ alkyl; K is C₁-C₁₅ alkyl; B is selected from a group consistingof O and S; A is selected from a group consisting of CN and(C═O)NR₃(R₄); and each stereoisomer is selected from a group consistingof E, Z, R, S, and a combination thereof, wherein the block copolymer isoperable to quench the excited state energy. Such substituent selectionsmay provide a greater ability of a compound to accept energy and/or havean excited state with a shorter lifetime. According to some embodiments,R₃ and R₄ may be independently C₁-C₁₅ alkyl; wherein n is a number from1 to 5,000; wherein m is a number from 0 to 20; and wherein R, R₁, R₂,R₃, and R₄ may be either straight chain or branched chain. According tosome embodiments, at least one block may have a structure according toFormula III:

wherein R₅ is C₁-C₃₀ alkyl; R₆ is selected from a group consisting of Hand C₁-C₁₅ alkyl; L is C₁-C₁₅ alkyl; D is selected from a groupconsisting of O and S; C is selected from a group consisting of CN and(C═O)NR₇(R₈); and each stereoisomer is selected from a group consistingof E, Z, R, S, and a combination thereof; wherein R₇ and R₈ areindependently C₁-C₁₅ alkyl; wherein o is a number from 1 to 5,000;wherein p is a number from 0 to 20; and wherein R₅, R₆, R₇ and R₈ may beeither straight chain or branched chain. Without being limited to anyparticular chemical mechanism of action, hydration of a phenolichydroxyl group when R and/or R₅ is a hydrogen may lead to an extendedlifetime of an excited state. Such extended excited state may result information of radicals and potential phototoxicity and/orphotodegradation. Further, an alkoxyl substitution at a para positionmay be critical and may allow for a shorter lifetime of anelectronically excited states of molecules. According to someembodiments, at least one block may have a structure according toFormula IV:

wherein R₉ and R₁₀ are independently C₁-C₁₅ alkyl, and E is selectedfrom a group consisting of O and S; wherein q is a number from 1 to5,000; and wherein r is a number from 0 to 20. According to someembodiments, at least one block may have a structure according toFormula V:

wherein F is selected from a group consisting of O and S; wherein s is anumber from 1 to 5,000; and wherein t is a number from 0 to 20. In someembodiments, a photostable photoactive composition may have at least oneblock having a structure according to Formula VI:

wherein R₁₁ and R₁₂ are independently C₁-C₁₅ alkyl, and G is selectedfrom a group consisting of O and S; wherein u is a number from 1 to5,000; and wherein v is a number from 0 to 20. In some embodiments,R₉═R₁₀, or R₁₁═R₁₂, but not both.

The present disclosure relates to photostable photoactive compositionsand methods of photostabilizing a photoactive composition. Suchcompositions may comprise one or more photoactive compounds that developan excited state when subjected to UV radiation. Photostabilizedphotoactive compositions may also comprise an excited state energyacceptor comprising one or more APP derivatives of Formula VII.According to this disclosure, APP derivatives of Formula VII are capableof photostabilizing photoactive compositions by serving as excited stateenergy acceptors. However, this disclosure is not limited to anyparticular mechanism by which APP derivatives of Formula VII are capableof photostabilizing photoactive compositions.

In some embodiments an APP analogue may comprise a structure accordingto Formula VII:

In some embodiments R₁₃ is selected from a group consisting of C₁-C₃₀alkyl (straight chain or branched chain). For example, R₁₃ may comprisea methyl, ethyl, isopropyl, n-butyl, sec-butyl, or tert-butyl group. Insome embodiments, R₁₃ is a hydrogen. Without being limited to anyparticular chemical mechanism of action, hydration of a phenolichydroxyl group when R₁₃ is a hydrogen may lead to an extended lifetimeof an excited state. Such extended excited state may result in formationof radicals and potential phototoxicity and/or photodegradation.Further, an alkoxyl substitution at a para position may be critical andmay allow for a shorter lifetime of the electronically excited states ofthese molecules.

According to some embodiments, R₁₄ is selected from a group consistingof C₁-C₁₅ alkoxyl (straight chain or branched chain), OH, or H. Forexample, R₁₄ may include, but is not limited to methoxyl, ethoxyl, OH,or H. In some embodiments, R₁₅ is selected from a group consisting of Hor C₁-C₁₅ alkoxyl (straight chain or branched chain). For example, R₁₅may include, but is not limited to methoxyl, ethoxyl, OH, or H. In someembodiments R₁₆ is selected from a group consisting of C₁-C₄₀ alkyl(straight chain or branched chain). For example, R₁₆ may include, but isnot limited to methyl, ethyl, propyl, butyl, pentyl, hexyl, or octyl. Insome embodiments, the APP derivatives of Formula I comprise the Zstereoisomer, the E stereoisomer, or combinations thereof.

In some embodiments N is selected from a group consisting of O or S. Insome embodiments, M is selected from the group consisting of C₁-C₁₅alkyl. Such selections may provide a greater ability by a compound toaccept energy and/or have an excited state with a shorter lifetime.

In some embodiments, J may be selected from a group consisting of CN or(C═O)NR₁₇(R₁₈), wherein R₁₇ and R₁₈ are independently selected fromC₁-C₁₅ alkyl (straight chain or branched chain). For example, R₁₇ andR₁₈ can include, but are not limited to methyl, ethyl, propyl, butyl.According to some embodiments of the disclosure, A does not include(C═O)O-alkyl. A material comprising a (C═O)O-alkyl substituent at A maybe thermodynamically unstable under basic conditions.

According to some embodiments, the present disclosure relates to methodsof photostabilizing a photoactive composition containing a blockcopolymer and at least one photoactive compound. In some embodiments, amethod may comprise (a) adding at least one photoactive compound in aneffective amount to the composition and (b) adding a block copolymeraccording to Formula I in an effective amount to the composition,wherein the block copolymer comprises a plurality of blocks. In someembodiments, methods may comprise a block copolymer that may be operableto quench an excited state energy and a photoactive composition mayprotect a substrate from oxidative stress caused by adsorption of lighthaving a wavelength in the wavelength range from about 280 nm to about400 nm.

The present disclosure, in some embodiments may comprise an APP blockcopolymer as described herein present at a concentration from about0.000001% by weight to about 20% by weight, based on a total weight of acomposition. In some embodiments, at least one photoactive compound maybe present at a concentration of about 1% to about 20%, based on a totalweight of a composition. In some embodiments, an APP block copolymer ispresent at a concentration comprising about 15% by weight, about 10% byweight, about 5% by weight, about 1% by weight, about 0.5% by weight,about 0.1% by weight, or a combination thereof, based on a total weightof a composition.

In some embodiments, a sunscreen, cosmetic, polymer, coating, ordermatological composition may comprise an APP block copolymer asdescribed herein present at a concentration of about 0.000001% by weightto about 20% by weight, based on a total weight of a composition. Insome embodiments, a concentration of an APP block copolymer is presentat a concentration comprising about 15% by weight, about 10% by weight,about 5% by weight, about 1% by weight, about 0.5% by weight, about 0.1%by weight, or a combination thereof, based on a total weight of acomposition.

The present disclosure relates, in some embodiments, to methods ofphotostabilizing a photoactive composition containing a block copolymerand at least one photoactive compound, wherein an APP block copolymer asdescribed herein may be present at a concentration of about 0.000001% byweight to about 20% by weight, based on a total weight of a composition.In some embodiments, an APP block copolymer may be present at aconcentration of about 1% by weight to about 20% by weight, based on atotal weight of a composition. In some embodiments, an APP blockcopolymer may be present at a concentration comprising about 15% byweight, about 10% by weight, about 5% by weight, about 1% by weight,about 0.5% by weight, about 0.1% by weight, or a combination thereof,based on a total weight of a composition.

The present disclosure, in some embodiments, may comprise blockcopolymer derivatives of Formula I that may stabilize photoactivecompounds that develop excited states when subjected to UV radiation. Insome embodiments, photoactive compounds may include dibenzoyl methanederivatives such as: 2-methyldibenzoylmethane; 4-methyldibenzoylmethane;4-isopropyldibenzoylmethane; 4-tert-butyldibenzoylmethane;2,4-dimethydibenzoylmethane; 2-5-dimethyl dibenzoylmethane;4,4′-diispropyl dibenzoylmethane; 4,4′-dimethoxy dibenzoylmethane;4-tert-butyl-4′-methoxy dibenzoylmethane;2-methyl-5-isopropyl-4′-methoxydibenzoylmethane;2-methyl-5-tert-butyl-4′-methoxydibenzoylmethane;2,4-dimethyl-4′-methoxydibenzoylmethane; and2,6-dimethyl-4-tert-butyl-4′-methoxydibenzoylmethane.

In some embodiments photoactive compounds may be alternatively describedas UV-absorbing compounds and/or UV filtering compounds. UV-absorbingcompounds may include octyl methoxycinnamate (OMC), octocrylene,salicylic acid esters (e.g., ethylhexyl salicylate and homomenthylsalicylate,), p-methoxycinnamic acid esters (e.g., ethylhexylmethoxycinnamate and isoamyl methoxycinnamate), avobenzone (also knownas butyl methoxydibenzoylmethane), oxybenzone, bis-ethylhexyloxyphenolmethoxyphenyl triazone, methylene bis-benzotriazolyltetramethylbutylphenol, 4-methylbenzylidene camphor, diethylaminohydroxyl benzoyl hexyl benzoate, drometrizole trisiloxane, ethylhexyltriazone, diethylhexyl butamido triazone, terephthalylidene dicamphorsulfonic acid and its salts, and menthyl anthranilate.

In some embodiments, photoactive compounds that develop excited stateswhen subjected to UV radiation may comprise p-aminobenzoic acid, itssalts, and its derivatives (ethyl, isobutyl, glyceryl esters;p-dimethylaminobenzoic acid); anthranilates (o-aminobenzoates; methyl,menthyl, phenyl, benzyl, phenylethyl, linalyl, terpinyl, andcyclohexenyl esters); salicylates (octyl, amyl, phenyl, benzyl,(+)-menthyl, (−)-menthyl, glyceryl, and dipropyleneglycol esters);cinnamic acid derivatives ((+)-menthyl, (−)-menthyl, and benzyl esters,alpha-phenyl cinnamonitrile; butyl cinnamoyl pyruvate); coumarinderivatives umbelliferone, methylumbelliferone,methylaceto-umbelliferone); camphor derivatives (3 benzylidene,4-methylbenzylidene, polyacrylamidomethyl benzylidene, benzalkoniummethylsulfate, benzylidene camphor sulfonic acid, and terephthalylidenedicamphor sulfonic acid); trihydroxycinnamic acid derivatives(esculetin, methylesculetin, daphnetin, and the glucosides, esculin anddaphnin); hydrocarbons (diphenylbutadiene, stilbene); dibenzalacetone;benzalacetophenone; naphtholsulfonates (sodium salts of2-naphthol-3,6-disulfonic and of 2-naphthol-6,8-disulfonic acids);dihydroxy-naphthoic acid and its salts; o- andp-hydroxydiphenyldisulfonates; coumarin derivatives (7-hydroxy,7-methyl, 3-phenyl); diazoles (2-acetyl-3-bromoindazole, phenylbenzoxazole, methyl naphthoxazole, various aryl benzothiazoles); quininesalts (bisulfate, sulfate, chloride, oleate, and tannate); quinolonederivatives (8-hydroxyquinoline salts, 2-phenylquinoline); hydroxy- ormethoxy-substituted benzophenones; uric acid derivatives; violuric acidderivatives; tannic acid and its derivatives; hydroquinone;benzophenones (oxybenzone, sulisobenzone, dioxybenzone, benzoresorcinol,octabenzone, 4-isopropyldibenzoylmethane, butyl methoxydibenzoylmethane,etocrylene, and 4-isopropyl-dibenzoylmethane); 2-ethylhexylp-methoxycinnamate; 4,4′-t-butyl methoxydibenzoylmethane; octyldimethylp-aminobenzoate; digalloyl trioleate; ethyl4-[bis(hydroxypropyl)]aminobenzoate; 2-ethylhexyl salicylate; glycerolp-aminobenzoate; 3,3,5-trimethylcyclohexylsalicylate; and combinationsthereof.

Photoactive compositions may include at least one UV-A radiationabsorbing (320-400 nm) photoactive compound and at least one UV-Bradiation absorbing (280-320 nm) photoactive compound. According to someembodiments, photoactive compounds that develop excited states whensubjected to UV radiation may comprise 4-methyldibenzoylmethane andderivatives thereof; octyl methoxycinnamate and derivatives thereof;octocrylene and derivatives thereof; p-methoxycinnamic acid esters andderivatives thereof;1-(4-methoxyphenyl)-3-(4-tert-butylphenyl)propane-1,3-dione andderivatives thereof; oxybenzone and derivatives thereof;bis-ethylhexyloxyphenol methoxyphenyl triazone and derivatives thereof;methylene bis-benzotriazolyl tetramethylbutylphenol and derivativesthereof; 4-methylbenzylidene camphor and derivatives thereof;diethylamino hydroxyl benzoyl hexyl benzoate and derivatives thereof;drometrizole trisiloxane and derivatives thereof; ethylhexyl triazone,diethylhexyl butamido triazone and derivatives thereof;terephthalylidene dicamphor sulfonic acid, its salts, and derivativesthereof, menthyl anthranilate and derivatives thereof; retinol andderivatives thereof; coenzyme Q and derivatives thereof; cholecalciferoland derivatives thereof; porphyrin and derivatives thereof, resveratroland derivatives thereof; p-aminobenzoic acid, its salts, and derivativesthereof; glyceryl esters; anthranilate and derivatives thereof; cinnamicacid and derivatives thereof, coumarin and derivatives thereof;trihydroxycinnamic acid and derivatives thereof; dibenzalacetonenaphtholsulfonate, its salts, and derivatives thereof; dibenzalacetoneand derivatives thereof; dihydroxy-naphthoic acid, its salts, andderivatives thereof; o-hydroxydiphenyldisulfonate, its salts, andderivatives thereof; diazole derivatives; quinine derivatives its,salts, and derivatives thereof; quinoline derivatives;hydroxyl-substituted benzophenone derivatives; quinolone derivatives;benzophenone derivatives; uric acid derivatives; quinine salts;hydroxydiphenyldisulfonate, its salts, and derivatives thereof; tannicacid and derivatives thereof; violuric acid and derivatives thereof;phenylbenzimidazole tetrasulfonate, its salts, and derivatives thereof;terephthalylidene dicamphor sulfonic acid, its salts, and derivativesthereof; benzalacetophenone naphtholsulfonate, its salts, andderivatives thereof; benzoic acid, its salts, and derivatives thereof;o-hydroxydiphenyldisulfonate, its salts, and derivatives thereof;p-naphthalate derivatives; methoxy-substituted uric acid derivatives;hydroquinone, its salts, and derivatives thereof; benzophenonederivatives; dihydroxycinnamic acid, its salts, and derivatives thereof;1, 3, 5-triazine derivatives; methylene bis-benzotriazolyltetramethylbutylphenol, it salts and derivatives thereof; titaniumdioxide and derivatives thereof; triazole and derivatives thereof; zincoxide; bis-ethylhexyloxyphenol methoxyphenyl triazine and its salts;salicylate and derivatives thereof; diethylamino hydroxyl benzoyl hexylbenzoate, its salts, and derivatives thereof; and combinations of theforegoing.

According some embodiments, photoactive compounds that develop excitedstates when subjected to UV radiation may comprise aminobenzoic acid,cinoxate, dioxybenzone, homosalate, menthyl anthranilate, octocrylene,octyl methoxycinnamate, octyl salicylate, oxybenzone, padimate 0,phenylbenzimidazole sulfonic acid, sulisobenzone, titanium dioxide,trolamine salicylate; zinc oxide, diethanolamine methoxycinnamate,ethyl-[bis(hydroxypropyl)] aminobenzoate, glyceryl aminobenzoate,4-isopropyl dibenzoylmethane, 4-methylbenzylidene camphor,terephthalylidene dicamphor sulfonic acid, sulisobenzone, camphorbenzalkonium methosulfate, homosalate, benzophenone, terephthalydenedicamphor sulfonic acid, benzylidene camphor sulfonic acid,polyacrylamidomethyl benzylidene camphor, PEG-25 PABA, isoamylp-methoxycinnamate, ethylhexyl triazone, drometrizole trisiloxane,diethylhexyl butamido triazone, 4-methylbenzylidene camphor, benzylidenecamphor, ethylhexyl salicylate, ethylhexyl dimethyl PABA, methylene bisbenztriazolyl tetramethylbutylphenol, disodium phenyl dibenzimidazoletetrasulfonate, bis ethylhexyloxyphenol methoxyphenol triazine,methylene bisbenzotriazolyl tetramethylbutylphenol,4-(2-oxo-3-bornylidenemethyl)benzene-sulfonic acid,2-methyl-5-(2-oxo-3-bornylidenemethyl)sulfonic acid and the saltsthereof, 2-(4′-diethylamino-2′-hydroxybenzoyl) benzoic acid hexyl ester,2,2′-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol),bisoctyltriazole, diethylhexyl 2,6-naphthalate, andbisethylhexyloxyphenol methoxyphenyl triazine.

A photoactive compound may be considered stable when, for example, afterabout a 30 Minimum Erythemal Dose (“MED”) irradiation, the photoactivecompound has retained at least about 90% of its original absorbance at awavelength, or over a range of wavelengths of interest (e.g., awavelength at which a photoactive compound has a peak absorbance, suchas 350-370 nm for Avobenzone). In some embodiments, a sunscreen, acosmetic, a polymer, a coating, or a dermatological composition mayinclude a plurality of photoactive compounds and may be consideredstable as a whole when, for example, after about a 30 MED irradiation,the sunscreen, cosmetic, or dermatological composition has retained atleast about 90% of its original absorbance at one or more wavelengths ofinterest (e.g., at or near a peak absorbance wavelength of a primaryphotoactive compound). According to some embodiments, a compositioncomprising an effective amount of at least one APP derivative mayinclude a concentration of at least one APP derivative, wherein afterabout a 30 MED irradiation, the composition retains at least about 90%of its original absorbance at one or more wavelengths of interest.

The present disclosure, in some embodiments may comprise at least onephotoactive compound as described herein present at a concentration ofabout 0.000001% by weight to about 20% by weight, based on a totalweight of a composition. In some embodiments, at least one photoactivecompound may be present at a concentration of about 1% by weight toabout 20% by weight, based on a total weight of a composition. In someembodiments, at least one photoactive compound may be present at aconcentration comprising about 15% by weight, about 10% by weight, about5% by weight, about 1% by weight, about 0.5% by weight, about 0.1% byweight, or a combination thereof, based on a total weight of acomposition.

In some embodiments, a sunscreen, cosmetic, polymer, coating, ordermatological composition may comprise at least one photoactivecompound as described herein present at a concentration of about0.000001% by weight to about 20% by weight, based on a total weight of acomposition. In some embodiments, a concentration of at least onephotoactive compound may be present at a concentration comprising about15% by weight, about 10% by weight, about 5% by weight, about 1% byweight, about 0.5% by weight, about 0.1% by weight, or a combinationthereof, based on a total weight of a composition.

The present disclosure relates, in some embodiments, to methods ofphotostabilizing a photoactive composition containing a block copolymerand at least one photoactive compound, the methods comprising at leastone photoactive compound as described herein present at a concentrationof about 0.000001% by weight to about 20% by weight, based on a totalweight of a composition. In some embodiments, at least one photoactivecompound may be present at a concentration of about 1% by weight toabout 20% by weight, based on a total weight of a composition. In someembodiments, at least one photoactive compound is present at aconcentration comprising about 15% by weight, about 10% by weight, about5% by weight, about 1% by weight, about 0.5% by weight, about 0.1% byweight, or a combination thereof, based on a total weight of acomposition.

According to some embodiments, a photoactive composition may include oneor more photoactive compounds, wherein the photoactive compound(s) mayact to absorb UV radiation and thereby protect a substrate comprising asunscreen, a cosmetic, a polymer, and a coating from effects of UVradiation. Further, application of a substrate comprising a photoactivecomposition to a surface comprising skin (e.g., animal or human), hair(e.g., animal or human), wood, metal, glass, and plastic, protects thesurface from effects of UV radiation. In some embodiments, a polymer maycomprise high-density polyethylenes, low-density polyethylenes,polytetrafluoroethenes, polyureas, polyamides, epoxy resins,polysaccharides, polyurethanes, polymethyl methacrylate, polystyrenes,polyamides, nylons, polypropylenes, rubbers, celluloses, polyvinylchlorides, polyesters, polycarbonates, and polyvinyl alcohols. Coatingsmay comprise adhesives, acrylic paint, latex paint, stains, caulk,sealants, urethanes, enamels, films, and inks. Photostable photoactivecompositions comprising an APP block copolymer may enhance protection ofa sunscreen against UV radiation, wherein application of said sunscreento a skin and/or a hair of an animal (e.g., human) may protect the skinand/or hair against UV radiation.

An absorption process may cause a photoactive compound to reach anexcited state, wherein the excited state is characterized by thepresence of excited electronic energy (e.g., singlet state energy ortriplet state energy), as compared to a ground state of the photoactivecompound. Once a photoactive compound reaches an excited state, thereexists a number of pathways by which the excited photoactive compoundcan dissipate its excess energy (e.g., singlet and/or triplet energy),however, many of those pathways adversely affect the ability of thephotoactive compound to further absorb UV radiation. For example, if thepathway results in a structural rearrangement of the photoactivecompound (e.g., De Mayo reaction and fragmentation). APP block copolymerderivatives may accept electronic excited state energy from UVabsorbers, providing photostability to photoactive compounds. In someembodiments, an acceptance of electronic excited state energy by an APPblock copolymer from a photoactive compound may result in thephotoactive compound returning to a ground state energy configuration oran at least partially lower energy state. In some embodiments, APP blockcopolymers may provide electronic excited state energy quenching ofUV-radiation absorbing compounds in compositions, the compositionscomprising sunscreen, cosmetic, polymer, coating, and dermatologicalformulations. Sunscreens, cosmetics, or dermatological compositions maybe used for coating a skin surface to protect skin from UV radiationdamage when exposed to sunlight, or other UV radiation. In someembodiments, sunscreen, cosmetic, or dermatological compositions includea UV-A radiation filter and/or a UV-B radiation filter compound and/or abroad-band filter compound, particularly a dibenzoylmethane derivativeUV-A radiation filter that is photostabilized by at least one APP blockcopolymer for protection of skin from UV-A and/or UV-B wavelengthradiation.

In some embodiments, APP block copolymers may be hydrophobic and may notbe water soluble. Waterproof sunscreen, cosmetic, or dermatologicalcompositions may comprise at least one hydrophobic APP block copolymeranalogue. In some embodiments, compositions and methods may comprise anoil phase. An oil phase may further comprise at least one polar solvent,wherein at least one polar solvent may increase a polarity of an oilphase of a composition including APP block copolymer derivatives. Insome embodiments, increasing a polarity of an oil phase of a compositionmay increase a photostability of photoactive compounds in a composition.In some embodiments, at least one polar solvent is present in anoil-phase of a composition, wherein the amount of polar solvent presentmay increase a dielectric constant of the oil-phase of the compositionto a dielectric constant of at least about 7. Enough polar solvent maybe present to raise a dielectric constant of an oil-phase of acomposition to at least about 8. In some embodiments, polar solventscomprise acetone, ethanol, n-butanol, isopropanol, acetonitrile, ethylacetate, dimethyl sulfoxide, water, and combinations thereof.

In some embodiments, sunscreen, cosmetic, or dermatological compositionsdescribed herein may comprise an APP block copolymer derivative and oneor more photoactive compounds. Compositions may include both UV-A andUV-B radiation absorbing photoactive compounds in a cosmeticallyacceptable carrier, optionally including additives, such as emollients,stabilizers, emulsifiers, and combinations thereof. Additives may beused in preparing a sunscreen, cosmetic, or dermatological compositionin an emulsion (oil-in-water or water-in-oil) from a composition thatincludes one or more photoactive compounds and a solvent or a solventcombination that includes one or more organic solvents and water. Anemulsion may be an oil-in-water emulsion, wherein an oil phase isprimarily formed from a mixture of a UV radiation filter compound(s),and may include a dibenzoylmethane derivative, such as Avobenzone, andone or more organic solvents.

In some embodiments, a composition comprising an APP block copolymer andat least one photoactive compound may be used for sunscreen, cosmetic,or dermatological compositions, wherein compositions treat, care,decorate, and/or cleanse skin and/or hair from an animal (e.g., human).Sunscreen, cosmetic, or dermatological compositions may comprisecosmetic auxiliaries such as those conventionally used in suchpreparations, such as preservatives, bactericides, perfumes, antifoamingagents, dyes, pigments which have a coloring effect, thickeners,moisturizers and/or humectants, fats, oils, waxes or other conventionalconstituents of a sunscreen, cosmetic, or dermatologic formulation,other conventional constituents comprising alcohols, polyols, polymers,foam stabilizers, electrolytes, organic solvents, silicone derivatives,or combinations thereof.

As will be understood by those skilled in the art who have the benefitof the instant disclosure, other equivalent or alternative compositionsand methods for formulating a photostable UV radiation absorbingcomposition comprising APP block copolymer derivatives can be envisionedwithout departing from the description contained herein. Accordingly,the manner of carrying out the disclosure as shown and described is tobe construed as illustrative only.

Persons skilled in the art may make various changes in the identity andquantity of components without departing from the scope of the instantdisclosure. Each disclosed method and method step may be performed inassociation with any other disclosed method or method step and in anyorder according to some embodiments. Where the verb “may” appears, it isintended to convey an optional and/or permissive condition, but its useis not intended to suggest any lack of operability unless otherwiseindicated. Persons skilled in the art may make various changes inmethods of preparing and using a composition of the disclosure. Forexample, a composition, device, and/or system may be prepared and orused as appropriate for animal and/or human use (e.g., with regard tosanitary, infectivity, safety, toxicity, biometric, and otherconsiderations). Elements, compositions, devices, systems, methods, andmethod steps not recited may be included or excluded as desired orrequired.

Also, where ranges have been provided, the disclosed endpoints may betreated as exact and/or approximations as desired or demanded by theparticular embodiment. Where the endpoints are approximate, the degreeof flexibility may vary in proportion to the order of magnitude of therange. For example, on one hand, a range endpoint of about 50 in thecontext of a range of about 5 to about 50 may include 50.5, but not 52.5or 55 and, on the other hand, a range endpoint of about 50 in thecontext of a range of about 0.5 to about 50 may include 55, but not 60or 75. In addition, it may be desirable, in some embodiments, to mix andmatch range endpoints. Also, in some embodiments, each figure disclosed(e.g., in one or more of the examples, tables, and/or drawings) may formthe basis of a range (e.g., depicted value+/−about 10%, depictedvalue+/−about 50%, depicted value+/−about 100%) and/or a range endpoint.With respect to the former, a value of 50 depicted in an example, table,and/or drawing may form the basis of a range of, for example, about 45to about 55, about 25 to about 100, and/or about 0 to about 100.Disclosed percentages are weight percentages except where indicatedotherwise.

These equivalents and alternatives along with obvious changes andmodifications are intended to be included within the scope of thepresent disclosure. Accordingly, the foregoing disclosure is intended tobe illustrative, but not limiting, of the scope of the disclosure asillustrated by the appended claims.

The title, abstract, background, and headings are provided in compliancewith regulations and/or for the convenience of the reader. They includeno admissions as to the scope and content of prior art and nolimitations applicable to all disclosed embodiments.

EXAMPLES

Some specific example embodiments of the disclosure may be illustratedby one or more of the examples provided herein.

UV light exposure is often measured in MED rather than a measurement oftime. MED relates to the minimal dosage of UV exposure required toresult in redness 24 hours after exposure. Although technically anindividualized measurement that would vary depending on the sensitivityof an individual's skin, MED measurements have been standardized withthe advent of UV bulbs and lamps.

Example 1: Comparing the Photostability of a Composition ContainingBMDBM and OMC

FIG. 1 illustrates the photoinstability of a composition containingBMDBM and OMC. As shown in FIG. 1, a composition containing anacetonitrile solution including 10 ppm BMDBM and 10 ppm OMC wasirradiated with 0 MED (before irradiation line) and 15 MED (afterirradiation line) of UV light. Absorption was measured for wavelengths250 nm to 500 nm in length. BMDBM absorbs wavelengths around 375 nm inlength, which can be seen as a distinct peak on the line illustratingthe composition which was not irradiated with UV light. However, asshown in FIG. 1, after 15 MED UV irradiation, the BMDBM peak at 375 nmis substantially diminished. Thus, FIG. 1 illustrates that the BMDBM inthe composition had a drastically reduced capability of absorbing lightafter exposure to 15 MED UV irradiation.

Example 2: Photostabilization of a Photoactive Composition with an APPAnalogue

FIG. 2 illustrates the photostabilization of a photoactive compositionby the addition of an APP analogue of Formula VII. As shown in FIG. 2, acomposition containing an acetonitrile solution of 10 ppm BMDBM, 10 ppmof OMC, and 5 ppm of an APP analogue of Formula VII was irradiated with0 MED (Before irradiation line) and 15 MED (After irradiation line) ofUV light. As shown in FIG. 2, the BMDBM peak at 375 nm is onlymoderately diminished after exposure of the composition to 15 MED (blueline). Thus, FIG. 2 illustrates that the APP analogue of Formula VII hada photostabilizing effect on the composition.

Example 3: Comparing the Stability of Compositions with and without APP

FIG. 3 illustrates the percentage of BMDBM remaining in compositionsafter irradiation with 15 MED of UV light. As shown in FIG. 3, only 2.9%of the BMDBM of a composition containing 10 ppm BMDBM and 10 ppm OMCremained capable of absorbing light at 375 nm after being irradiatedwith 15 MED of UV light. By contrast, approximately 76.8% of the BMDBMof a composition containing 10 ppm BMDBM, 10 ppm OMC, and 5 ppm of anAPP analogue of Formula VII retained the ability to absorb light at 375nm. Thus, as illustrated in FIG. 3, APP derivatives of Formula VII arecapable of photostabilizing photoactive compositions.

Example 4: Phosphorescence Measurement in Ethanol Glass at 77K

Phosphorescence lifetimes were measured at 77 K exciting with pulsesfrom a Lambda Physik dye laser (FL3002; Laser dye: Stilbene 3) which waspumped with a Lambda Physik Excimer laser (Lextra 50) (FIG. 4). Thephosphorescence was collected and isolated using lenses andmonochromators (H10 for Vis spectral range and 1681B for NIR spectralrange; Jobin-Yvon Inc.) and focused onto Hamamatzu photomultiplier tubes(PMT) (R928 for the visible spectral range and H9170-45 for NIR spectralrange). The photocurrent from the PMT was amplified (SR 560, StanfordResearch Systems) and stored on a digital oscilloscope (TDS 360,Tektronix). We estimate the lifetime measurement error to be 5%.Phosphorescence spectra in ethanol glass at 77K. Methyl iodide (MEI) wasadded to increase the phosphorescence yields for APP-2 (33% Mel), APP-3(20% Mel) and CMPP (20% Mel). The phosphorescence for APP-2 was veryweak. APP-3 and CMPP are may quench triplet states of both, the keto andenol form of avobenzone by energy transfer. APP-2 may quench tripletstates of the keto form as seen in FIG. 4.

Example 5: Ketone Triplet State Quenching by APP Derivatives

The nanosecond flash photolysis system employs the a Quanta Ray DCR 2ANd:YAG laser (third [=355 nm] harmonic, 8-nanoseconds at full width athalf maximum (ns fwhm), typical laser energy=10-15 mJ/pulse at 20 Hz),and a Bruker broad band preamplifier with a response time of 60 ns forexcitation. A pulsed Xenon lamp, combined with an ISA H10 monochromator,serves as the monitoring system (See FIGS. 5-7). Typically data acquiredafter 10-15 laser pulses were averaged to produce each experimentaltrace both in the kinetic experiments and in the acquisition of atransient absorption spectra. Quartz cells having cross sections of 1×1cm were used. Laser flash photolysis of keto-avobenzone (266 nm, 5 nspulse width) were carried out in deoxygenated acetonitrile solutions. Todetermine the quenching rate constant of triplet keto-avobenzone, decaytraces of the triplet absorption of keto-avobenzone in the absence andpresence of varying concentrations of APPs were recorded.Keto-avobenzone was generated by photolysis of enol-avobenzone at 350nm.

What is claimed is:
 1. A photostable photoactive composition comprising:(a) at least one photoactive compound that develops within itself anexcited state energy when subjected to UV radiation, and (b) a blockcopolymer comprising a plurality of blocks, and having a structureaccording to Formula I:H₃C-V-W-X-Y-Z—CH₃ wherein the plurality of blocks comprises: at leastone block having a structure according to Formula II:

wherein: R is C₁-C₃₀ alkyl; R₁ is selected from the group consisting ofH, OH, and C₁-C₁₅ alkoxyl; R₂ is selected from the group consisting of Hand C₁-C₁₅ alkyl; K is C₁-C₁₅ alkyl; B is selected from the groupconsisting of O and S; A is selected from the group consisting of CN and(C═O)NR₃(R₄); and each stereoisomer is selected from the groupconsisting of E, Z, R, S, and a combination thereof; wherein R₃ and R₄are independently C₁-C₁₅ alkyl; wherein n is a number from 1 to 5,000;wherein m is a number from 0 to 20; wherein R, R₁, R₂, R₃, and R₄ may beeither straight chain or branched chain; at least one block having astructure according to Formula III:

wherein: R₅ is C₁-C₃₀ alkyl; R₆ is selected from the group consisting ofH and C₁-C₁₅ alkyl; L is C₁-C₁₅ alkyl; D is selected from the groupconsisting of O and S; C is selected from the group consisting of CN and(C═O)NR₇(R₈); and each stereoisomer is selected from the groupconsisting of E, Z, R, S, and a combination thereof; wherein R₇ and R₈are independently C₁-C₁₅ alkyl; wherein o is a number from 1 to 5,000;wherein p is a number from 0 to 20; wherein R₅, R₆, R₇ and R₈ may beeither straight chain or branched chain; at least one block having astructure according to Formula IV:

wherein: R₉ and R₁₀ are independently C₁-C₁₅ alkyl, and E is selectedfrom the group consisting of O and S; wherein q is a number from 1 to5,000; wherein r is a number from 0 to 20; and at least one block havinga structure according to Formula V:

wherein: F is selected from the group consisting of O and S; wherein sis a number from 1 to 5,000; wherein t is a number from 0 to 20; whereinthe block copolymer is operable to quench the excited state energy.
 2. Aphotostable photoactive composition according to claim 1, wherein atleast one block has a structure according to Formula VI:

wherein: R₁₁ and R₁₂ are independently C₁-C₁₅ alkyl, and G is selectedfrom the group consisting of O and S; wherein u is a number from 1 to5,000; wherein v is a number from 0 to 20; wherein R₉═R₁₀, or R₁₁═R₁₂,but not both.
 3. A photostable photoactive composition according toclaim 1, wherein the block copolymer is present at a concentration ofabout 1% by weight to about 20% by weight, based on a total weight ofthe composition.
 4. A photostable photoactive composition according toclaim 1, wherein the block copolymer is present at a concentrationcomprising about 15% by weight, about 10% by weight, about 5% by weight,about 1% by weight, or a combination thereof, based on the total weightof the composition.
 5. A photostable photoactive composition accordingto claim 1, wherein the at least one photoactive compound comprises4-methyldibenzoylmethane and derivatives thereof; octyl methoxycinnamateand derivatives thereof; octocrylene and derivatives thereof;p-methoxycinnamic acid esters and derivatives thereof;1-(4-methoxyphenyl)-3-(4-tert-butylphenyl)propane-1,3-dione andderivatives thereof; oxybenzone and derivatives thereof;bis-ethylhexyloxyphenol methoxyphenyl triazone and derivatives thereof;methylene bis-benzotriazolyl tetramethylbutylphenol and derivativesthereof; 4-methylbenzylidene camphor and derivatives thereof;diethylamino hydroxyl benzoyl hexyl benzoate and derivatives thereof;drometrizole trisiloxane and derivatives thereof; ethylhexyl triazone,diethylhexyl butamido triazone and derivatives thereof;terephthalylidene dicamphor sulfonic acid, its salts, and derivativesthereof, menthyl anthranilate and derivatives thereof; retinol andderivatives thereof; coenzyme Q and derivatives thereof; cholecalciferoland derivatives thereof; porphyrin and derivatives thereof, resveratroland derivatives thereof; p-aminobenzoic acid, its salts, and derivativesthereof; glyceryl esters; anthranilate and derivatives thereof; cinnamicacid and derivatives thereof, coumarin and derivatives thereof;trihydroxycinnamic acid and derivatives thereof; dibenzalacetonenaphtholsulfonate, its salts, and derivatives thereof; dibenzalacetoneand derivatives thereof; dihydroxy-naphthoic acid, its salts, andderivatives thereof; o-hydroxydiphenyldisulfonate, its salts, andderivatives thereof; diazole derivatives; quinine derivatives, itssalts, and derivatives thereof; quinoline derivatives;hydroxyl-substituted benzophenone derivatives; quinolone derivatives;benzophenone derivatives; uric acid derivatives; quinine salts;hydroxydiphenyldisulfonate, its salts, and derivatives thereof; tannicacid and derivatives thereof; violuric acid and derivatives thereof;phenylbenzimidazole tetrasulfonate, its salts, and derivatives thereof;terephthalylidene dicamphor sulfonic acid, its salts, and derivativesthereof; benzalacetophenone naphtholsulfonate, its salts, andderivatives thereof; benzoic acid, its salts, and derivatives thereof;o-hydroxydiphenyldisulfonate, its salts, and derivatives thereof;p-naphthalate derivatives; methoxy-substituted uric acid derivatives;hydroquinone, its salts, and derivatives thereof; benzophenonederivatives; dihydroxycinnamic acid, its salts, and derivatives thereof;1, 3, 5-triazine derivatives; methylene bis-benzotriazolyltetramethylbutylphenol, its salts, and derivatives thereof; titaniumdioxide and derivatives thereof; triazole and derivatives thereof; zincoxide; bis-ethylhexyloxyphenol methoxyphenyl triazine and its salts;salicylate and derivatives thereof; diethylamino hydroxyl benzoyl hexylbenzoate, its salts, and derivatives thereof; and combinations of theforegoing.
 6. A photostable photoactive composition according to claim1, wherein the at least one photoactive compound is present at aconcentration of about 0.000001% by weight to about 20% by weight, basedon the total weight of the composition.
 7. A photostable photoactivecomposition according to claim 1, wherein the at least one photoactivecompound is present at a concentration comprising about 15% by weight,about 10% by weight, about 5% by weight, about 1% by weight, about 0.5%by weight, about 0.1% by weight, or a combination thereof, based on thetotal weight of the composition.
 8. A photostable photoactivecomposition according to claim 1, wherein said composition includes anoil phase having a dielectric constant of at least about
 8. 9. Aphotostable photoactive composition according to claim 1, wherein saidcomposition may enhance protection of at least one polymer against UVradiation, the at least one polymer comprising polyvinyl chloride,polystyrene, low-density polyethylene, high-density polyethylene,polyamides, nylon, polypropylene, rubber, and cellulose.
 10. Aphotostable photoactive composition according to claim 1, wherein saidcomposition may enhance protection of at least one coating against UVradiation, the at least one coating comprising adhesives, acrylic paint,latex paint, stains, caulk, sealants, urethanes, enamels, films, andinks.
 11. A photostable photoactive composition according to claim 1,wherein said composition may enhance protection of a sunscreen againstUV radiation, wherein application of said sunscreen to a skin of ananimal may protect the skin against UV radiation.
 12. A photostablephotoactive composition according to claim 1, wherein said compositionmay enhance protection of a cosmetic against UV radiation, whereinapplication of said cosmetic to a skin or a hair of an animal mayprotect the skin or the hair against UV radiation.
 13. A photostablephotoactive composition according to claim 9, wherein application ofsaid coating to a surface may protect the surface against UV radiation.14. A method of photostabilizing a photoactive composition containing ablock copolymer and at least one photoactive compound, the methodcomprising: (a) adding the at least one photoactive compound in aneffective amount to the composition, wherein the at one photoactivecompounds develops within itself an excited state energy when subjectedto UV radiation; and (b) adding the block copolymer in an effectiveamount to the composition, wherein the block copolymer comprises aplurality of blocks, and has a structure according to Formula I:H₃C-V-W-X-Y-Z—CH₃ wherein the plurality of blocks comprises: at leastone block having a structure according to Formula II:

wherein: R is C₁-C₃₀ alkyl; R₁ is selected from the group consisting ofH, OH, and C₁-C₁₅ alkoxyl; R₂ is selected from the group consisting of Hand C₁-C₁₅ alkyl; K is C₁-C₁₅ alkyl; B is selected from the groupconsisting of O and S; A is selected from the group consisting of CN and(C═O)NR₃(R₄); and each stereoisomer is selected from the groupconsisting of E, Z, R, S, and a combination thereof; wherein R₃ and R₄are independently C₁-C₁₅ alkyl; wherein n is a number from 1 to 5,000;wherein m is a number from 0 to 20; wherein R, R₁, R₂, R₃, and R₄ may beeither straight chain or branched chain; at least one block having astructure according to Formula III:

wherein: R₅ is C₁-C₃₀ alkyl; R₆ is selected from the group consisting ofH and C₁-C₁₅ alkyl; L is C₁-C₁₅ alkyl; D is selected from the groupconsisting of O and S; C is selected from the group consisting of CN and(C═O) NR₇ (R₈); and each stereoisomer is selected from the groupconsisting of E, Z, R, S, and a combination thereof; wherein R₇ and R₈are independently C₁-C₁₅ alkyl; wherein o is a number from 1 to 5,000;wherein p is a number from 0 to 20; wherein R₅, R₆, R₇ and R₈ areindependently selected from C₁-C₁₅ alkyl; at least one block having astructure according to Formula IV:

wherein: R₉ and R₁₀ are independently C₁-C₁₅ alkyl, and E is selectedfrom the group consisting of O and S; wherein q is a number from 1 to5,000; wherein r is a number from 0 to 20; and at least one block has astructure according to Formula V:

wherein: F is selected from the group consisting of O and S; wherein sis a number from 1 to 5,000; and wherein t is a number from 0 to 20;wherein the block copolymer is operable to quench the excited stateenergy; and wherein the photoactive composition protects a substratefrom oxidative stress caused by absorption of light having a wavelengthin the wavelength range of about 280 nm to about 400 nm.
 15. A methodaccording to claim 14, wherein at least one block has a structureaccording to Formula VI:

wherein: R₁₁ and R₁₂ are independently C₁-C₁₅ alkyl, and G is selectedfrom the group consisting of O and S; wherein u is a number from 1 to5,000; wherein v is a number from 0 to 20; wherein R₉═R₁₀, or R₁₁═R₁₂,but not both.
 16. A method according to claim 14, wherein the substratecomprises a sunscreen, a cosmetic, a polymer, and a coating.
 17. Amethod according to claim 14, wherein application of said sunscreen to askin of an animal thereby protects the skin against UV radiation.
 18. Amethod according to claim 14, wherein the polymer comprises high-densitypolyethylene, low-density polyethylene, polystyrene, polyamides, nylon,polypropylene, rubber, cellulose, polyvinyl chloride, and polyvinylalcohol.
 19. A method according to claim 14, wherein the coatingcomprises stains, caulk, sealants, urethanes, enamels, films, adhesives,acrylic paints, latex paints, and inks.
 20. A method according to claim14, wherein the block copolymer is present at a concentration of about1% by weight to about 20% by weight, based on a total weight of thecomposition.
 21. A method according to claim 14, wherein the blockcopolymer is present at a concentration comprising about 15% by weight,about 10% by weight, about 5% by weight, about 1% by weight, or acombination thereof, based on the total weight of the composition.
 22. Amethod according to claim 14, wherein the at least one photoactivecompound comprises 4-methyldibenzoylmethane and derivatives thereof;octyl methoxycinnamate and derivatives thereof; octocrylene andderivatives thereof; p-methoxycinnamic acid esters and derivativesthereof; 1-(4-methoxyphenyl)-3-(4-tert-butylphenyl)propane-1,3-dione andderivatives thereof; oxybenzone and derivatives thereof;bis-ethylhexyloxyphenol methoxyphenyl triazone and derivatives thereof;methylene bis-benzotriazolyl tetramethylbutylphenol and derivativesthereof; 4-methylbenzylidene camphor and derivatives thereof;diethylamino hydroxyl benzoyl hexyl benzoate and derivatives thereof;drometrizole trisiloxane and derivatives thereof; ethylhexyl triazone,diethylhexyl butamido triazone and derivatives thereof;terephthalylidene dicamphor sulfonic acid, its salts, and derivativesthereof, menthyl anthranilate and derivatives thereof; retinol andderivatives thereof; coenzyme Q and derivatives thereof; cholecalciferoland derivatives thereof; porphyrin and derivatives thereof, resveratroland derivatives thereof; p-aminobenzoic acid, its salts, and derivativesthereof; glyceryl esters; anthranilate and derivatives thereof; cinnamicacid and derivatives thereof, coumarin and derivatives thereof;trihydroxycinnamic acid and derivatives thereof; dibenzalacetonenaphtholsulfonate, its salts, and derivatives thereof; dibenzalacetoneand derivatives thereof; dihydroxy-naphthoic acid, its salts, andderivatives thereof; o-hydroxydiphenyldisulfonate, its salts, andderivatives thereof; diazole derivatives; quinine derivatives, itssalts, and derivatives thereof; quinoline derivatives;hydroxyl-substituted benzophenone derivatives; quinolone derivatives;benzophenone derivatives; uric acid derivatives; quinine salts;hydroxydiphenyldisulfonate, its salts, and derivatives thereof; tannicacid and derivatives thereof; violuric acid and derivatives thereof;phenylbenzimidazole tetrasulfonate, its salts, and derivatives thereof;terephthalylidene dicamphor sulfonic acid, its salts, and derivativesthereof; benzalacetophenone naphtholsulfonate, its salts, andderivatives thereof; benzoic acid, its salts, and derivatives thereof;o-hydroxydiphenyldisulfonate, its salts, and derivatives thereof;p-naphthalate derivatives; methoxy-substituted uric acid derivatives;hydroquinone, its salts, and derivatives thereof; benzophenonederivatives; dihydroxycinnamic acid, its salts, and derivatives thereof;1, 3, 5-triazine derivatives; methylene bis-benzotriazolyltetramethylbutylphenol, its salts, and derivatives thereof; titaniumdioxide and derivatives thereof; triazole and derivatives thereof; zincoxide; bis-ethylhexyloxyphenol methoxyphenyl triazine and its salts;salicylate and derivatives thereof; diethylamino hydroxyl benzoyl hexylbenzoate, its salts, and derivatives thereof; and combinations of theforegoing.
 23. A method according to claim 14, wherein the at least onephotoactive compound is present at a concentration of about 0.000001% byweight to about 20% by weight, based on the total weight of thecomposition.
 24. A method according to claim 14, wherein the at leastone photoactive compound is present at a concentration comprising about15% by weight, about 10% by weight, about 5% by weight, about 1% byweight, about 0.5% by weight, about 0.1% by weight, or a combinationthereof, based on the total weight of the composition.
 25. A methodaccording to claim 14, wherein said photoactive composition includes anoil phase having a dielectric constant of at least about
 7. 26. A methodaccording to claim 14, wherein said photoactive composition includes anoil phase having a dielectric constant of at least about
 8. 27. A methodaccording to claim 13, wherein application of said cosmetic to a skin ora hair of an animal thereby protects the skin or hair against UVradiation.
 28. A method according to claim 13, wherein application ofsaid sunscreen to a skin of an animal thereby protects the skin againstUV radiation.
 29. A cosmetic or dermatological composition for coating askin to protect the skin from oxidative stress caused by absorption oflight having a wavelength in the wavelength range of about 280 nm toabout 400 nm, the composition comprising: (a) at least one photoactivecompound that develops within itself an excited state energy whensubjected to UV radiation, (b) a block copolymer comprising a pluralityof blocks, having a structure according to Formula I:H₃C-V-W-X-Y-Z—CH₃ wherein the plurality of blocks comprises: at leastone block having a structure according to Formula II:

wherein: R is C₁-C₃₀ alkyl; R₁ is selected from the group consisting ofH, OH, and C₁-C₁₅ alkoxyl; R₂ is selected from the group consisting of Hand C₁-C₁₅ alkyl; K is C₁-C₁₅ alkyl; B is selected from the groupconsisting of O and S; A is selected from the group consisting of CN and(C═O) NR₃ (R₄); and each stereoisomer is selected from the groupconsisting of E, Z, R, S, and a combination thereof; wherein R₃ and R₄are independently C₁-C₁₅ alkyl; wherein n is a number from 1 to 5,000;wherein m is a number from 0 to 20; wherein R, R₁, R₂, R₃, and R₄ may beeither straight chain or branched chain; at least one block having astructure according to Formula III:

wherein: R₅ is C₁-C₃₀ alkyl; R₆ is selected from the group consisting ofH and C₁-C₁₅ alkyl L is C₁-C₁₅ alkyl; D is selected from the groupconsisting of O and S; C is selected from the group consisting of CN and(C═O)NR₇(R₈); and each stereoisomer is selected from the groupconsisting of E, Z, R, S, and a combination thereof; wherein R₇ and R₈are independently C₁-C₁₅ alkyl; wherein o is a number from 1 to 5,000;wherein p is a number from 0 to 20; wherein R₅, R₆, R₇ and R₈ areindependently C₁-C₁₅ alkyl; at least one block having a structureaccording to Formula IV:

wherein: R₉ and R₁₀ are independently C₁-C₁₅ alkyl, and E is selectedfrom the group consisting of O and S; wherein q is a number from 1 to5,000; wherein r is a number from 0 to 20; and at least one block havinga structure according to Formula V:

wherein: F is selected from the group consisting of O and S; wherein sis a number from 1 to 5,000; wherein t is a number from 0 to 20; whereinthe block copolymer is operable to quench the excited state energy. 30.A cosmetic or dermatological composition of claim 29, wherein at leastone block has a structure according to Formula VI:

wherein: R₁₁ and R₁₂ are independently C₁-C₁₅ alkyl, and G is selectedfrom the group consisting of O and S; wherein u is a number from 1 to5,000; wherein v is a number from 0 to 20; wherein R₉═R₁₀, or R₁₁═R₁₂,but not both.
 31. A cosmetic or dermatological composition of claim 29,wherein the skin surface comprises human skin and animal skin.
 32. Acosmetic or dermatological composition of claim 29, wherein the blockcopolymer is present at a concentration of about 1% by weight to about20% by weight, based on a total weight of the composition.
 33. Acosmetic or dermatological composition of claim 29, wherein the blockcopolymer is present at a concentration comprising about 15% by weight,about 10% by weight, about 5% by weight, about 1% by weight, or acombination thereof, based on the total weight of the composition.
 34. Acosmetic or dermatological composition of claim 29, wherein the at leastone photoactive compound comprises 4-methyldibenzoylmethane andderivatives thereof; octyl methoxycinnamate and derivatives thereof;octocrylene and derivatives thereof; p-methoxycinnamic acid esters andderivatives thereof;1-(4-methoxyphenyl)-3-(4-tert-butylphenyl)propane-1,3-dione andderivatives thereof; oxybenzone and derivatives thereof;bis-ethylhexyloxyphenol methoxyphenyl triazone and derivatives thereof;methylene bis-benzotriazolyl tetramethylbutylphenol and derivativesthereof; 4-methylbenzylidene camphor and derivatives thereof;diethylamino hydroxyl benzoyl hexyl benzoate and derivatives thereof;drometrizole trisiloxane and derivatives thereof; ethylhexyl triazone,diethylhexyl butamido triazone and derivatives thereof;terephthalylidene dicamphor sulfonic acid, its salts, and derivativesthereof, menthyl anthranilate and derivatives thereof; retinol andderivatives thereof; coenzyme Q and derivatives thereof; cholecalciferoland derivatives thereof; porphyrin and derivatives thereof, resveratroland derivatives thereof; p-aminobenzoic acid, its salts, and derivativesthereof; glyceryl esters; anthranilate and derivatives thereof; cinnamicacid and derivatives thereof, coumarin and derivatives thereof;trihydroxycinnamic acid and derivatives thereof; dibenzalacetonenaphtholsulfonate, its salts, and derivatives thereof; dibenzalacetoneand derivatives thereof; dihydroxy-naphthoic acid, its salts, andderivatives thereof; o-hydroxydiphenyldisulfonate, its salts, andderivatives thereof; diazole derivatives; quinine derivatives, itssalts, and derivatives thereof; quinoline derivatives;hydroxyl-substituted benzophenone derivatives; quinolone derivatives;benzophenone derivatives; uric acid derivatives; quinine salts;hydroxydiphenyldisulfonate, its salts, and derivatives thereof; tannicacid and derivatives thereof; violuric acid and derivatives thereof;phenylbenzimidazole tetrasulfonate, its salts, and derivatives thereof;terephthalylidene dicamphor sulfonic acid, its salts, and derivativesthereof; benzalacetophenone naphtholsulfonate, its salts, andderivatives thereof; benzoic acid, its salts, and derivatives thereof;o-hydroxydiphenyldisulfonate, its salts, and derivatives thereof;p-naphthalate derivatives; methoxy-substituted uric acid derivatives;hydroquinone, its salts, and derivatives thereof; benzophenonederivatives; dihydroxycinnamic acid, its salts, and derivatives thereof;1, 3, 5-triazine derivatives; methylene bis-benzotriazolyltetramethylbutylphenol, its salts, and derivatives thereof; titaniumdioxide and derivatives thereof; triazole and derivatives thereof; zincoxide; bis-ethylhexyloxyphenol methoxyphenyl triazine and its salts;salicylate and derivatives thereof; diethylamino hydroxyl benzoyl hexylbenzoate, its salts, and derivatives thereof; and combinations of theforegoing.
 35. A cosmetic or dermatological composition of claim 29,wherein the at least one photoactive compound is present at aconcentration of about 0.000001% by weight to about 20% by weight, basedon the total weight of the composition.
 36. A cosmetic or dermatologicalcomposition of claim 29, wherein the at least one photoactive compoundis present at a concentration comprising about 15% by weight, about 10%by weight, about 5% by weight, about 1% by weight, about 0.5% by weight,about 0.1% by weight, or a combination thereof, based on the totalweight of the composition.
 37. A cosmetic or dermatological compositionof claim 29, wherein said composition includes an oil phase having adielectric constant of at least about 8.